EP0377533B1 - Procédé de préparation d'un polymère à base de chlorure de vinyle - Google Patents

Procédé de préparation d'un polymère à base de chlorure de vinyle Download PDF

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Publication number
EP0377533B1
EP0377533B1 EP90400021A EP90400021A EP0377533B1 EP 0377533 B1 EP0377533 B1 EP 0377533B1 EP 90400021 A EP90400021 A EP 90400021A EP 90400021 A EP90400021 A EP 90400021A EP 0377533 B1 EP0377533 B1 EP 0377533B1
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EP
European Patent Office
Prior art keywords
polymerization
vinyl chloride
monomer
weight
amount
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP90400021A
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German (de)
English (en)
Other versions
EP0377533A2 (fr
EP0377533A3 (fr
Inventor
Genji Noguki
Kouzou Kuwabara
Shigehiro Hoshida
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shin Etsu Chemical Co Ltd
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Shin Etsu Chemical Co Ltd
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Publication of EP0377533A2 publication Critical patent/EP0377533A2/fr
Publication of EP0377533A3 publication Critical patent/EP0377533A3/fr
Application granted granted Critical
Publication of EP0377533B1 publication Critical patent/EP0377533B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/02—Monomers containing chlorine
    • C08F14/04—Monomers containing two carbon atoms
    • C08F14/06—Vinyl chloride

Definitions

  • the present invention relates to a method for the preparation of a vinyl chloride-based polymer, referred to as a PVC hereinafter, of high quality useful as a molding material of various kinds of shaped articles. More particularly, the invention relates to a method for the preparation of a PVC having a greatly improved particle configuration by preventing foams rising in the polymerization reactor during the polymerization reaction.
  • a problem in this method of operating a reflux condenser for the removal of the heat of polymerization is that foaming sometimes takes place on the polymerization mixture in the reactor so that the particles of the PVC resin produced may have a low bulk density with a foamy structure.
  • the PVC resin product thus prepared may contain coarse particles which may be retained on a screen of 48 mesh having a mesh opening of 0.297 mm according to JIS Z 8801 in the test of the particle size distribution.
  • foamy resin particles are sometimes responsible for the scale deposition on the walls of the polymerization reactor in the upper part to seriously decrease the productivity.
  • foams on the polymerization mixture can be destroyed mechanically by rotating foam-breaking blades provided on the stirrer shaft. This method is not always very effective in practice because of the deposition of the foam debris on to the foam-breaking blades and inner walls of the polymerization reactor resulting in scale deposition.
  • the present invention accordingly has an object to provide a novel and improved efficient method for the preparation of a high-quality PVC resin without the above described problems in the prior art.
  • the present invention provides an improvement in the polymerization of vinyl chloride monomer or a monomer mixture mainly composed of vinyl chloride in an aqueous polymerization medium contained in a polymerization reactor equipped with a reflux condenser for the removal of the heat of polymerization, which improvement comprises admixing the aqueous polymerization mixture with additives comprising (a) from 0.002 to 0.007 part by weight of a partially saponified polyvinyl alcohol having a degree of saponification in the range from 20 to 50% by moles and an average degree of polymerization in the range from 200 to 400 and (b) from 0.001 to 0.01 part by weight of a defoaming agent, each amount being per 100 parts by weight of the vinyl chloride monomer or the monomer mixture mainly composed of vinyl chloride, at a moment when the cumulative amount of the heat of polymerization removed through the reflux condenser does not exceed 10% of the overall heat of polymerization which should be evolved when the whole amount of the vinyl chloride monomer or the mono
  • the characteristic feature of the improvement according to the invention consists in the addition of specific additives to the polymerization mixture at a specified moment.
  • the first of the additives is a partially saponified polyvinyl alcohol having a degree of saponification in the range from 20 to 50% by moles and an average degree of polymerization in the range from 200 to 400, which is added to the polymerization mixture in an amount in the range from 0.002 to 0.007 part by weight per 100 parts by weight of the vinyl chloride monomer or the monomer mixture mainly composed of vinyl chloride.
  • the added amount thereof is too small, the defoaming activity to be exhibited by the defoaming agent cannot be fully exhibited so that the resultant PVC resin product may contain a considerable amount of foamy particles.
  • the PVC resin product may have a somewhat decreased bulk density.
  • the partially saponified polyvinyl alcohol should have the above mentioned relatively low degree of saponification. When the degree of saponification thereof is too high, the synergistic effect thereof with the defoaming agent is decreased so that the amount of scale deposition may eventually be increased. Further, the partially saponified polyvinyl alcohol should have the above mentioned specific average degree of polymerization. When the average degree of polymerization is too large, the synergistic effect thereof with the defoaming agent is also decreased so that the resultant PVC resin product may contain a considerable amount of foamy particles.
  • the second additive to be added to the polymerization mixture in combination with the above described specific polyvinyl alcohol is a defoaming agent which is preferably a silicone-based one such as silicone fluids, e.g., dimethyl polysiloxanes and diphenyl polysiloxanes.
  • the silicone-based defoaming agent is preferably of an aqueous emulsion type obtained by emulsifying a silicone fluid in an aqueous medium with admixture of from 0.05 to 0.4 part by weight of a finely divided silica powder having the surface rendered hydrophobic per 100 parts by weight of the silicone fluid.
  • the amount of this defoaming agent added to the polymerization mixture is in the range from 0.001 to 0.01 part by weight excepting the water as the medium of the aqueous emulsion per 100 parts by weight of the vinyl chloride monomer or the monomer mixture mainly composed of vinyl chloride.
  • the added amount thereof is too small, the defoaming activity to be exhibited thereby is insufficient so that the resultant PVC resin product may contain a considerable amount of foamy particles.
  • Increase in the amount thereof over the above mentioned upper limit has no particular advantageous effect on the defoaming power rather with an economical disadvantage and other problems.
  • the above described two additives must be introduced into the polymerization mixture at a specified moment. Namely, the moment of the addition of the additives should be not later than the moment when the cumulative amount of the heat of polymerization removed through the reflux condenser does not exceed 10% of the overall heat of polymerization which should be evolved when the whole amount of the vinyl chloride monomer or the monomer mixture mainly composed of vinyl chloride has been polymerized. It is preferable that the additives are added to the polymerization mixture before the start of removal of the heat of polymerization through the reflux condenser. When the additives are added belatedly, no satisfactory defoaming can be obtained to allow the foams rising in the polymerization reactor resulting in a large amount of scale deposition on the reactor walls.
  • the above described improvement of the invention is applicable to the polymerization process of vinyl chloride monomer or a monomer mixture mainly composed of vinyl chloride in an aqueous medium regardless of the types of the process including suspension polymerization and emulsion polymerization, of which particularly satisfactory results could be obtained in the suspension polymerization.
  • the suspension polymerization, to which the inventive improvement is applied is not limited to the homopolymerization of vinyl chloride monomer alone but to the copolymerization of vinyl chloride with other comonomers copolymerizable therewith provided that the major fraction, e.g., 50% by weight or more, of the monomer mixture is vinyl chloride.
  • Examples of the comonomer copolymerizable with vinyl chloride include: vinyl esters, e.g., vinyl acetate and vinyl propionate; esters of acrylic and methacrylic acids, e.g., methyl acrylate and ethyl acrylate; olefins, e.g., ethylene and propylene; vinyl ethers, e.g., lauryl vinyl ether and isobutyl vinyl ether; maleic anhydride; acrylonitrile; styrene and vinylidene chloride.
  • vinyl esters e.g., vinyl acetate and vinyl propionate
  • esters of acrylic and methacrylic acids e.g., methyl acrylate and ethyl acrylate
  • olefins e.g., ethylene and propylene
  • vinyl ethers e.g., lauryl vinyl ether and isobutyl vinyl ether
  • maleic anhydride acrylon
  • the polymerization initiator added to the polymerization mixture can be selected from monomer-soluble and water-soluble ones.
  • the monomer-soluble polymerization initiator include: percarbonate compounds, e.g., diisopropylperoxy dicarbonate, di-2-ethylhexylperoxy dicarbonate and di(ethoxyethylperoxy) dicarbonate; perester compounds, e.g., tert-butylperoxy neo-decanoate, tert-butylperoxy pivalate, tert-hexylperoxy pivalate and ⁇ -cumylperoxy neodecanoate; peroxide compounds, e.g., acetyl cyclohexylsulfonyl peroxide, 2,4,4-trimethylpentyl-2-peroxy phenoxy acetate, 3,5,5-trimethylhexanoyl peroxide and lauroyl peroxide; and azo compounds.
  • water-soluble polymerization initiator examples include potassium persulfate, ammonium persulfate, hydrogen peroxide and cumene hydroperoxide. These polymerization initiators can be used either singly or as a combination of two kinds or more according to need.
  • the aqueous polymerization medium contains a suspending agent in order to obtain a stable suspension of the monomer or monomer mixture in the medium.
  • the suspending agent can be selected from known ones including: water-soluble cellulose ethers e.g., methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and hydroxypropyl methyl cellulose; poly(acrylic acid); water-soluble natural polymers, e.g., gelatine; monomer-soluble surface active agents, e.g., sorbitan monolaurate, sorbitan trioleate, sorbitan monostearate, glycerin tristearate and ethylene oxide-propylene oxide block copolymers; water-soluble surface active agents, e.g., polyoxyethylene sorbitan monolaurate, polyoxyethylene glycerin oleate and sodium lauryl sulfate; calcium carbonate; calcium phosphate and sodium dodecylbenz
  • the suspension polymerization of the monomer or monomer mixture with the inventive improvement can be performed according to a conventional procedure well established in the art excepting the addition of the above specified specific additives at a specified moment, including the ways for the introduction of the various ingredients of the polymerization mixture, i.e. the aqueous medium, monomer or monomer mixture, suspending agent and polymerization initiator, as well as the relative amounts of these ingredients and the schedule of the polymerization temperature control.
  • the polymerization mixture is further admixed with various kinds of known additives conventionally used in the polymerization of vinyl chloride monomer including polymerization moderators, chain transfer agents, pH controlling agents, gelation improvers, antistatic agents, crosslinking agents, stabilizers, fillers, antioxidants, buffer agents and scale-deposition inhibitors according to need.
  • additives conventionally used in the polymerization of vinyl chloride monomer including polymerization moderators, chain transfer agents, pH controlling agents, gelation improvers, antistatic agents, crosslinking agents, stabilizers, fillers, antioxidants, buffer agents and scale-deposition inhibitors according to need.
  • the improvement of the invention serves to establish an efficient defoaming method against the foams rising above the polymerization mixture in the course of the polymerization reaction of vinyl chloride monomer in an aqueous medium so that an industrially great advantage is obtained thereby.
  • Run No. 1 to No. 6 Six polymerization runs, referred to as Run No. 1 to No. 6 hereinbelow, were performed in the following manner, Thus, into a stainless steel-made polymerization reactor of 2000 liter capacity equipped with a stirrer, reflux condenser and jacket for passing cooling-heating water were introduced 900 kg of deionized water, 420 g of a partially saponified polyvinyl alcohol having a degree of saponification of 80% by moles and an average degree of polymerization of 2000 and 260 g of 2-ethylhexylperoxy dicarbonate.
  • the polymerization mixture in the reactor was admixed with 100 g in the form of a 30% by weight solution in methyl alcohol of a partially saponified polyvinyl alcohol having a degree of saponification of 40% by moles and an average degree of polymerization of 300, referred to as the additive A hereinbelow, and 60 g of an aqueous emulsion containing 50% by weight of a dimethyl polysiloxane and 0.1% by weight of a finely divided silica powder rendered hydrophobic on the surface, referred to as the additive B hereinbelow, at a moment when the temperature of the polymerization mixture just had reached 57 °C.
  • Runs No. 2 to No. 6 undertaken for comparative purpose were substantially the same as in Run No. 1 described above except that: the amount of the additive A was increased to 200 g in Run No. 2; the amount of the additive A was decreased to 20 g in Run No. 3; the additive A was entirely omitted in Run No. 4; the additive B was omitted in Run No. 5; and both of the additives A and B were omitted in Run No. 6.
  • the polymerizate slurry was discharged out of the reactor and processed according to a conventional procedure to give 520 kg of a dry PVC resin as the product.
  • the polymerization reactor after discharge of the polymerizate slurry was examined to check the amount of polymer scale deposition on the inner walls. The results were recorded as shown in Table 1 below according to three ratings of criterion including A for the aboslute absence of polymer scale deposition, B for a small amount of polymer scale deposition and C for a large amount of polymer scale deposition.
  • the PVC resin products were subjected to the tests of the bulk density in g/cm3 according to the procedure specified in JIS K 6721 and the amount of coarse foamy particles in % by weight retained on a screen of 48 mesh fineness specified in JIS Z 8801. The results are shown also in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (4)

  1. Procédé de polymérisation d'un monomère de chlorure de vinyle ou d'un mélange de monomères constitué principalement de chlorure de vinyle dans un milieu aqueux de polymérisation contenu dans un réacteur de polymérisation équipé d'un condenseur à reflux pour l'élimination de la chaleur de polymérisation qui consiste à mélanger le mélange aqueux de polymérisation à des additifs comprenant (a) de 0,002 à O,007 parties en poids d'un alcool polyvinylique partiellement saponifié présentant un degré de saponification situé dans un domaine de 20 à 50% en moles et un degré moyen de polymérisation dans un domaine de 200 à 400 et (b) de O,001 à O,O1 parties en poids d'un agent de démoussage, chaque partie étant pour 100 parties en poids du monomère de chlorure de vinyle ou de mélange de monomères essentiellement composé de chlorure de vinyle, à un moment où la quantité cumulée de la chaleur de polymérisation éliminée par l'intermédiaire du condenseur à reflux, n'excède pas 10% de la chaleur totale de polymérisation qui serait impliquée si la quantité totale de monomère de chlorure de vinyle ou le mélange de monomères composé essentiellement de chlorure de vinyle avait été polymérisée.
  2. Procédé selon la revendication 1 dans lequel les additifs (a) et (b) sont ajoutés au mélange de polymérisation avant de mettre en service le condenseur à reflux.
  3. Procédé selon la revendication 1 selon lequel l'additif (b) est un agent de démoussage à base de silicone.
  4. Procédé selon la revendication 3 dans lequel l'agent de démoussage à base de silicone est une émulsion aqueuse d'un fluide de silicone contenant de 0,05 à 0,4 parties en poids de poudre de silice finement divisée pour 100 parties en poids du fluide de silicone.
EP90400021A 1989-01-05 1990-01-04 Procédé de préparation d'un polymère à base de chlorure de vinyle Expired - Lifetime EP0377533B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP784/89 1989-01-05
JP64000784A JPH02180908A (ja) 1989-01-05 1989-01-05 塩化ビニル系重合体の製造方法

Publications (3)

Publication Number Publication Date
EP0377533A2 EP0377533A2 (fr) 1990-07-11
EP0377533A3 EP0377533A3 (fr) 1991-01-16
EP0377533B1 true EP0377533B1 (fr) 1993-07-21

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ID=11483324

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Application Number Title Priority Date Filing Date
EP90400021A Expired - Lifetime EP0377533B1 (fr) 1989-01-05 1990-01-04 Procédé de préparation d'un polymère à base de chlorure de vinyle

Country Status (5)

Country Link
US (1) US5087678A (fr)
EP (1) EP0377533B1 (fr)
JP (1) JPH02180908A (fr)
ES (1) ES2058826T3 (fr)
PT (1) PT92789B (fr)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5849831A (en) * 1996-04-19 1998-12-15 Kuraray Co., Ltd. Process for producing vinyl resin
BR9709266A (pt) * 1996-05-24 1999-08-10 Bp Chem Int Ltd Processo para polimerização de olefinas
US6197878B1 (en) 1997-08-28 2001-03-06 Eastman Chemical Company Diol latex compositions and modified condensation polymers
JP2002538259A (ja) 1999-03-03 2002-11-12 イーストマン ケミカル カンパニー ポリアミド／エマルジョンポリマーブレンド
WO2000052083A1 (fr) 1999-03-03 2000-09-08 Eastman Chemical Company Compositions de diol polymere silicone et melanges de polycondensat/silicone polymere
EP1187870A1 (fr) 1999-06-18 2002-03-20 Eastman Chemical Company Melanges nylon 6/silicone
BR0011719A (pt) 1999-06-18 2002-03-05 Eastman Chem Co Processo para fabricação de uma mistura de polìmeros tipo amida/polìmero silicone, produto, e, mistura de polìmeros
JP4421715B2 (ja) 1999-10-28 2010-02-24 日本合成化学工業株式会社 ビニル系樹脂の製造方法
JP2003246808A (ja) 2002-02-26 2003-09-05 Shin Etsu Chem Co Ltd 塩化ビニル系重合体の製造方法
TWI256954B (en) 2003-01-30 2006-06-21 Nippon Synthetic Chem Ind Dispersing agent comprising vinyl alcohol polymer having conjugated double bonds in its molecule
JP5019778B2 (ja) * 2006-04-14 2012-09-05 新第一塩ビ株式会社 塩化ビニル系重合体の製造方法
KR101534399B1 (ko) 2012-12-18 2015-07-09 주식회사 엘지화학 현탁 중합을 이용한 염화비닐계 수지의 제조방법
EP3075750B1 (fr) * 2013-11-28 2020-01-08 Hanwha Chemical Corporation Procédé pour la préparation de résine à base de chlorure de vinyle
KR101987438B1 (ko) 2015-05-13 2019-06-11 주식회사 엘지화학 염화비닐 중합체의 제조 방법

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB907973A (en) * 1960-06-07 1962-10-10 Ici Ltd Polymerisation process
GR76488B (fr) * 1981-04-01 1984-08-10 Goodrich Co B F
KR860001114B1 (ko) * 1981-06-22 1986-08-13 다까다 다까시 염화비닐 수지의 제조방법
US4464519A (en) * 1982-06-07 1984-08-07 Air Products And Chemicals, Inc. Vinyl chloride-propylene copolymers having increased porosity
JPS60158206A (ja) * 1984-01-27 1985-08-19 Toyo Soda Mfg Co Ltd 塩化ビニルの懸濁重合法
JPS61115908A (ja) * 1984-11-10 1986-06-03 Kanegafuchi Chem Ind Co Ltd 塩化ビニル系樹脂の製法

Also Published As

Publication number Publication date
PT92789A (pt) 1990-07-31
US5087678A (en) 1992-02-11
EP0377533A2 (fr) 1990-07-11
PT92789B (pt) 1995-12-29
ES2058826T3 (es) 1994-11-01
JPH02180908A (ja) 1990-07-13
EP0377533A3 (fr) 1991-01-16

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